Production of nitrophosphate fertilizer

ABSTRACT

Nitrophosphate fertilizer is produced by the nitric acid digestion of phosphate rock. The pH of the initial digestion solution is raised to the range of about 1.8 to 2.5 by ammonia addition, to precipitate impurities including a major portion of fluoride and iron phosphate. The solid precipitate is filtered from the clear solution, and the solid filter cake is calcined at elevated temperature to volatilize fluorine and decompose iron phosphate into a nitric acid-insoluble form. The calcined cake is digested with nitric acid to recover phosphate and aluminum values in solution, and the resulting slurry is filtered and the solid filter cake containing iron compounds and silica is discarded. The clear filtrate is combined with the initial clear solution previously formed by filtration to remove solid fluoride and iron impurities, and the combined solution is preferably further acidified to reduce the PH to a low and highly acid value. A soluble salt such as ammonium sulfate or potassium sulfate, which has an anion which forms an insoluble solid salt with the calcium cation, is added to the combined solution, and an insoluble solid calcium salt is precipitated. Filtration removes the solid calcium salt, and ammonia is added to the remaining solution to raise the pH and precipitate remaining impurities. After removal of precipitated solid impurities by filtration, the final solution is processed by water removal to produce solid nitrophos fertilizer, usually together with ammonium nitrate as a co-product.

[22] Filed:

United States Patent [191 Strelzoff et al.

1 PRODUCTION OF NITROPHOSPHATE FERTILIZER [751' Inventors: Samuel Strelzoff, New York, N.Y.;

Sydney Atkin, Springfield, NJ.

[73] Assignee: Chemical Construction Corporation,

New York, NY.

Sept. 5, 1972 [211 Appl. No.: 286,444

Related US. Application Data [60] Continuation of Ser. No. 85,956, Nov. 2, 1970, abandoned, which is a division of Scr. No. 766,139, Oct. 9, 1968, Pat. No. 3,582,313.

Primary ExaminerSamih NqZ aharna Assistant ExaminerR-ichard Barnes Attorney-J. L. Chaboty [451 Jan. 15, 1974 [57] ABSTRACT Nitrophosphate fertilizer is, produced by the nitric acid digestion of phosphate rock. The pH of the initial digestion solution is raised to the range of about 1.8 to 2.5 by ammonia addition, to precipitate impurities including a major portion of fluoride and iron phosphate. The solid precipitate is filtered from the clear solution, and the solid filter cake is calcined at elevated temperature to volatilize fluorine and decompose iron phosphate into a nitric acid-insoluble form. The calcined cake is digested with nitric acid to recover phosphate and aluminum values in solution, and the resulting slurry is filtered and the solid filter cake containing iron compounds and silica is discarded. The clear filtrate is combined with the initial clear solution previously formed-by filtration to remove solid fluoride and iron impurities, and the combined solution is preferably further acidified to reduce the PH to a low and highly acid value. A soluble salt such as ammonium' sulfate or potassium sulfate, which has an anion which forms an insoluble solid salt with the calcium cation, is added to the combined solution, and

' an insoluble solid calcium salt is precipitated. Filtra 2 Claims, 1 Drawing Figure PAIENTEUJAM 15 m4 3, 785.797

SAMUEL STRELZOFF SYDNEY ATKIN INVENTORS.

AGENT PRODUCTION OF NITROPI'IOSPI'IATE FERTILIZER This is a continuation of application Ser. No. 85,956 filed Nov. 2, 1970, now abandoned which is a division of application Ser. No. 766,139 filed Oct. 9, 1968, now issued as U.S. Pat. No. 3,582,313.

BACKGROUND OF THE INVENTION 1. Field of the Invention The invention relates to the digestion of phosphate rock, shale or the like with nitric. acid, and the processing of the resulting solution with ammonia and a sulfate salt or the like, to respectively precipitate impurities and solid calcium sulfate, so as to produce a final purified solution from which a solid nitrophosphate fertilizer containing a high proportion of water-soluble phosphate is produced by water removal. The term phosphate rock as employed herein will be understood to encompass the various types of phosphate shale and other phosphatic materials of similar compositions, as well as phosphate rock per se.

2. Description of Prior Art ,The conventional procedure for the processing of phosphate rock to produce soluble phosphates for usage as fertilizers entails the treatment of the ground rock withsulfuric acid. The resultant digestion of the rock, which takes place over a time interval in a den or the like, results in the production of a normal superphosphate product, in which the phosphate values are solubilized and thereby become available to. plants when applied to the soil. In some instances, a more highly concentrated product is produced, by reacting the phosphate rock with aqueous sulfuric acid to produce a slurry of solid calcium sulfate in phosphoric acid solution. The solid calcium sulfate is removed by filtration, and the phosphoric acid solution is concentrated and reacted with further phosphate rock to produce triple superphosphate fertilizer.

The acidulation or digestion of phosphate rock with nitric acid has been described in U. S. Pat. No. 2,689,175 and U. S. Pat. application No. 680,757 filed Nov. 6, 1967 now abandoned. In the patented process, the ground phosphate rock is reacted with aqueous nitric acid, and the sulfate radical required for the elimination of calcium viathe'formation of solid calcium sulfate is supplied by adding an ammonium sulfate solution to the reaction mixture. These reagents are combined in the properproportion to produce a slurry of filterable calcium sulfate, or'gypsum, in an aqueous solution of phosphoric acid and ammonium nitrate. The slurry is filtered, and the clear solution is ammoniated and concentrated in stages, to principally produce ammonium phosphateand ammonium nitrate. French Pat. No. 705,887 provides a similar procedure, and descriptions of prior commercial techniques are given in Chemical Engineering, V. 74 No. 22, datedOct. 23, 1967, at pages 86-88, 90, 134-136. The recovery of valuable byproducts such as aluminum and uranium values from phosphatic material, specifically leached 'zone phosphates, is described in U. S. Pat. No.

SUMMARY OF THE, INVENTION In the present invention, a nitrophosphate product having high availability and water-solubility of phosphate values is produced, by the nitric acid acidulation of phosphate rock and subsequent ammoniation in an improved process sequence which features ammoniation of the initial digestion solution to precipitate impurities such as fluorine and iron, calcining of the precipitate to volatilize fluorine and convert iron to an acidinsoluble state, and nitric acid digestion of the calcined precipitate to solubilize and recover phosphate and aluminum values.

The feed phosphate rock, which may be initially ground to a powder or the like to aid in reaction, is digested with a first nitric acid-stream to form a solution containing dissolved phosphate. Ammonia is added to the solution to raise the pH of the solution to the range of about 1.8 to 2.5, which causes the formation of a solid precipitate containing most of the fluoride and iron phosphate impurities. The solid precipitate is separated from the clear solution and calcined at an elevated temperature generally in the range of 500C to 1000C, to volatilize fluorine-containing impurities and convert iron phosphate to acid-insoluble compounds by thermal decomposition.- The calcined precipitate is digested with a second nitric acid stream, to solubilize and dissolve phosphate and aluminum values. Residual solid material from this second digestion step, consisting mostly of insoluble iron compounds and silica, is discarded.- The clear liquid solution from the digestion of the calcined precipitate is added to the initial clear solution, and the pH of the combined clear solution may be lowered below 1.0 by the addition of further nitric acid. In any case, a soluble salt such as ammonium sulfate or potassium sulfate, which 'has an anion which forms an insoluble solid salt with the calcium cation, is added to the solution; so that the calcium nitrate in the combined solution is reacted to form a soluble nitrate and an insoluble solid calcium salt, such as calcium sulfate,which is removed from the solution. Ammonia is then added to the clear resulting solution, to raise the solution pH to the range of about 3.0 to about 4.5 and form a solid precipitate containing impuritieswhich is filtered from the solution. The final clear solution principally contains dissolved ammonium phosphate, mostly present as mono-ammonium acid phosphate, together with ammonium nitrate, and is processed by water removal to produce a nitrophos product. The nitrophos is generally produced by partial vacuum evaporation and crystallization, to produce a solid nitrophos precipitate in an aqueous ammonium nitrate mother liquor, which is separated from, the solid nitrophos and further concentrated to produce a substantially anhydrous ammonium nitrate melt which is prilled or otherwise processed to form discrete particles of solid am monium nitrate fertilizer.

The process of the presentinvention provides several salient novel features and advantages. The calcining step is highly important, because the calcining of the first ammoniation precipitate serves to volatilize more than 80% ofthe fiuorin e and decompose the iron phos-- phate, thus making the iron insoluble in the following redigestion step. The process permits the recovery of aluminum, uranium and rare earths values from the second ammoniation precipitate, typically by such procedures as described in U. S. Pat. No. 3,126,249. In this respect, after recovery of byproduct metals values, the

residual solution can be recycled to the present process to recover phosphate values. A relatively pure calcium sulfate or gypsum by-product can be produced, which is suitable for usage in the manufacture of building materials or compositions or the like. It has been determined that the filtration rates of the various slurries and precipitates in the process of the present invention are improved, as compared to prior art procedures, principally because the calcining step destroys the gelatinous slimes or the like which are formed or present in conventional processes for acid digestion of phosphate rock. A nitrophosphate product is produced in which more than 90 percent of the total phosphate is water soluble. In this respect, the removal of impurities such as fluorine, iron and calcium helps to prevent the reversion of phosphate in the final nitrophosphate product to the citrate-insoluble state. As will appear infra, a feed-grade dicalcium phosphate co-product may also be readily produced in conjunction with the present invention by usage of a portion of one of the process streams in accordance with the procedure of U. S. Pat. application No. 680,757 filed Nov. 6, 1967. Finally, the co-product ammonium nitrate forms a superior prilled product when the mother liquor solution is concentrated to an anhydrous melt and prilled, because the presence of small amounts of ammonium sulfate and ammonium phosphate in the final solid prills produces ties in an improved manner during the processing of phosphate rock with nitric acid.

A further object is to improve filtration rates of slurries during the processing of phosphate rock with nitric acid, in which precipitation from solutions is obtained by ammoniation or by the addition of a soluble salt having an anion which forms an insoluble solid salt with the calcium cation.

An additional object is to produce a nitrophos product in which most of the phosphate is in a water-soluble form, by the nitric acid acidulation of phosphate rock and subsequent ammoniation in two stages.

An object is to recover aluminum, uranium and rare earths values from phosphate rock in a concentrated by-product precipitate, during the nitric acid digestion of phosphate rock and subsequent ammoniation.

Still another object is to produce relatively pure byproduct gypsum during the nitric acid digestion of phosphate rock to produce nitrophosphate fertilizer.

Still a further object is to produce an improved form of ammonium nitrate prill composition during the nitric acid digestion of phosphate rock followed by ammoniation and separation of solid nitrophosphate from residual aqueous ammonium nitrate mother liquor.

Finally, an object is to provide a process for the production of nitrophos by the nitric acid digestion of phosphate rock in which feed grade dicalcium phosphate may be produced as a co-product of the process by selective ammoniation of a portion of an intermediate purified process stream.

These and other objects and advantages of the present invention will become evident from the description which follows.

DESCRIPTION OF THE DRAWING AND PREFERRED EMBODIMENTS Referring now to the drawing, a flowsheet of a preferred embodiment of the invention is presented. Ground phosphate rock stream 1 and aqueous nitric acid stream 2 are passed into digester 3, and the phosphate rock is digested and solubilized in unit 3. In addition to the reaction oftricalcium phosphate with nitric acid, small amounts of calcium carbonate and calcium fluoride present in stream 1 will-react with stream 2 to yield calcium nitrate and volatile off-gases such as carbon dioxide and hydrogen fluoride. A portion of the hydrogen fluoride reacts and remains in the liquid phase as combined fluorine, either as a fluoride or silicofluoride. The phosphate rock stream 1 will generally analyze in the range of about 25 percent to 38 percent or higher equivalent phosphorus pentoxide content, about 45 percent to 50 percent equivalent calcium oxide content, and about 2.5 percent to 4 percent equivalent fluv orine content, all in percentages by weight. The aqueous nitric acid stream 2 will generally contain in the range of about 20 percent to percent nitric acid content by weight, and sufficient flow rate of stream 2 relative to stream l is provided to maintain a pH in the range of about 0.3 to 1.5 unit 3. A temperature level generally in the range of about 55C to C is maintained within digester 3, and agitator or stirrer 4 is provided to circulate the reactants within unit 3 and produce a uniform solution, which may contain a small amount of slimy sludge insoluble in the acid solution. As mentioned supra, the slimy sludge is entrained in the initial precipitate and is eliminated in the calcining step, as will appear infra.

The aqueous solution 5 discharged from unit 3 principally contains calcium nitrate and an acid salt of calcium phosphate, generally monocalcium phosphate. Stream '5 is passed into ammoniation vessel 6 together with anhydrous or aqueous ammonia stream 7, which serves to raise the pH of the solution to a level generally in the range of about 1.8 to about 2.5, and to form a solid precipitate containing impurities such as fluorides and iron phosphate, together with the undigested slimy sludge. The resulting slurry stream 8 discharged from unit 6 is passed to solids filter 9, from which a solid filter cake stream 10 is removed and processed in accordance with the present invention.

Stream 10 contains calcium phosphate values, together with fluoride and iron phosphate impurities, a small proportion of aluminum values and the slimy residual sludge from digestion in unit 3. Stream 10 is passed into calciner 11, which generally consists of a rotary kiln or the like. Fuel stream 12, which usually consists of a fluid hydrocarbon fuel such as residual oil, fuel oil or natural gas, is passed into kiln 11, together with combustion air stream 13, and the combustion of stream 12 within unit 11 serves to generate a highly elevated temperature within kiln l 1, generally in the range of about 500C to.l000C. Solids filter cake stream 10 is calcined within unit 11, with resultant volatilization of most of the contained fluorine or fluoride compounds, which are discharged from kiln 11 in flue gas stream 14. In this manner, the discharge of stream 14 serves to eliminate a major portion of the fluorine from the subsequent processing steps and products. In addition, iron phosphate contained in the solids feed is converted to insoluble iron compounds in unit 11.

The resultant calcined filter cake solids stream 15 discharged from unit 11 is passed into digester 16 together with aqueous nitric acid stream 17. Unit 16 is similar in configuration and function to unit 3 described supra, and serves to digest and solubilize a major portion of steam 15, thus most of the phosphate and aluminum values in stream are dissolved into solution in unit 16 while iron compounds and silica remain in a solid undissolved state. A temperature level generally in the range of about 60 C to 90C is maintained in unit 16. The resulting slurry stream 18 discharged from unit 16 is passed to solids filter 19, from which a solid filter cake stream 20 is removed and discharged to waste. Stream 20 principally contains silica and iron compounds derived from stream 15 and the discharge of stream 20 thus serves to eliminate a major portion of the iron from the subsequent processing steps and products.

A clear solution stream 2 l co nt aining dissolved phosphate and aluminum values is removed from filter unit 19 and passed to solution combining and acidification vessel 22. Returning to filter unit 9, a clear aqueous solution stream 23 containing dissolved calcium nitrate, ammonium nitrate and phosphate values in the form of phosphoric acid and monoammonium acid phosphate is removed from unit 9. Stream 23 is preferably divided into stream 24, which is processed for the recovery of feed grade dicalcium phosphate in a manner to be described infra, and stream 25, which is passed to solution combining vessel 22 for combination with stream 21. The combined liquid phase in vessel 22 will generally have a pH below 2.5, and the pH of the combined solution is preferably adjusted to a value below 1.0 and preferably in the range of 0.3 to 0.7 by adding concentrated aqueous nitric acid stream 26 to vessel 22. Stream 26 will generally contain in the range of about 35 percent to 70 percent nitric acid content by weight.

The resulting acidified solutionstream 27 ieissssa from vessel 22 is now passed to conversion vessel 28, in which calcium ions are precipitated as a solid calcium salt by the addition of a soluble salt to the solution, which soluble salt has an anion which forms an insoluble solid salt with the calcium cation in the solution. The preferred soluble salt added to vessel 28 via stream 29 is ammoniumsulfate or potassium sulfate, however other soluble sulfates, carbonates such as ammonium carbonate, or the like may be employed as' phoric acid is produced in unit 28. The pH of the slurryin unit 28 is maintained in the range of about 0.5 to 2.0, and the temperature ofthe slurry is generally in the range of about 50C to 100C. The resulting slurry stream 30 discharged from unit 28 is passed to solids filter 31, from which a solid filter cake stream 32 is'removed. Stream 32 consists of relatively pure calcium sulfate or gypsum, and may be discharged to waste or employed in the manufacture of building materials or compositions or the like. The removal of stream 32 serves to eliminate most of the calcium from the subsequent processing steps and products.

A clear aqueous solution stream 33 containing dissolved ammonium nitrate, phosphoric acid and monoammonium acid phosphate is discharged from unit 31 and passed to ammoniation vessel 34, to which ammonia is added via stream 35 which raises the solution pH to the range of about 3.0 to 4.5 and precipitates an impurity-laden solids phase. In addition, the anhydrous or aqua ammonia stream 35 reacts within unit 34 with free phosphoric acid in the process solution, to form further monoammonium phosphate. A minor proportion of diammonium phosphate may form in solution at higher pH values. In any case, the resulting slurry stream 36 discharged from unit 34 is passed to solids filter 37, from which a solids filter cake stream 38 is discharged. Solids stream 38 contains a minor amount of phosphate values, together with concentrated proportions of impurities including aluminum, uranium and rare earths values. Stream 38 may be processed in accordance with the procedure of U. S. Pat. No. 3,126,249, to recover aluminum and uranium values.

A clear aqueous solution stream 39 is discharged from unit 37. Stream 39 is now relatively free of impurities such as fluorine, iron and calcium, and consists primarily of an aqueous solution containing dissolved ammonium nitrate and monoammonium acid phosphate. Because of the elimination of impurities as described supra, the subsequent solid nitrophos fertilizer product produced from stream 39 by water removal, as will appear infra, is relatively pure and reversion of phosphate values to a citrate-insoluble form is substantially prevented. Stream 39 is now passed to evaporator 40, which in most cases consists of a vacuum crystallizer which is heated by steam coil 41. Water vapor is removed from unit 40 via stream 42, which generally extends to a source of vacuum such as a steam jet exhauster. The removal of water in unit 40 causes the selective precipitation of nitrophosphate crystals consisting primarily of monoammonium phosphate, in an aqueous mother liquor-solution principally containing dissolved ammonium nitrate. The resulting slurry stream 43 discharged from unit 40 is passed to solids filter 44, from which solid filter cake stream 45 consisting of product nitrophos fertilizer principally containing monoammonium phosphate is passed to product utilization.

A clear mother liquor stream 46 is also removed from filter 44. Stream 46 consists essentially of an aqueous ammonium nitrate solution, andstream 46 is now preferably passed to evaporator 47 for heating'via steam coils 48 to produce a substantially anhydrous ammonium nitrate melt for prilling.

Returning to solids filter 9, a portion of the discharged clear solution stream 23 is preferably utilized via stream 24 for the production of feed grade dicalcium phosphate co-product. In this case, sufficient ammonia will be added to unit 6 via stream7 to produce a somewhat higher pH in the range of about 2.1 to 2.5 in unit 6, so as to attain greater precipitation of impurities in unit 6 for removal via stream 10, with solution stream 23 consequently being at a higher pH of 2.1 to 2.5 and therefore being relatively impurity-free. Stream 24 is withdrawn as a portion of stream 23, and is an aqueous solution containing dissolved calcium nitrate, ammonium nitrate and phosphate values in the form of phosphoric acid and monoammonium acid phosphate, in equilibrium with monocalcium phosphate. Stream 24 is passed into neutralizer vessel 49 together with ammonia stream 50, which serves to raise the solution pH 5 to a level generally in the range of about 3.0 to 6.0, and

to precipitate solid and relatively pure crystalline dicalcium phosphate in aqueous solution. The resulting slurry stream 51 discharged from unit 49 is passed to solids filter 52, from which solid'filter cake stream 53 consisting of substantially pure or feed grade dicalcium phosphate is removed and passed to product utilization.

A clear solution stream 54 containing dissolved calcium nitrate and ammonium nitrate is discharged from unit 52, and passed to conversion vessel 55, in which calcium ions are precipitated as solid calcium carbonate by the in situ formation of ammonium carbonate in solution. Ammonia stream 56 and carbon dioxide stream 57 are passed into unit 55, and essentially form ammonium carbonate in the aqueous solution, which reacts with dissolved calcium nitrate to form solid calcium carbonate and further dissolved ammonium nitrate. The slurry stream 58 discharged from unit 55 is passed into solids filter 59, from which solid calcium carbonate filter cake stream 60 is discharged to waste disposal.

The clear solution stream 61 discharged from unit 59 consists of an aqueous ammonium nitrate solution, which is passed to concentrator 47 together with stream 46 as described supra. The combined aqueous ammonium nitrate solution in-unit 47 is evaporated to produce a concentrated solution or substantially anhydrous melt, by circulating steam or other heating medium through coil 48. Evaporated water vapor is discharged from unit 47 via stream 62. Unit 47 may be of analternative falling film evaporator configuration in practice, in which case streams 46 and 61 would flow downwards as a liquid film on the inner surfaces of vertical tubes, through which a heated air stream is circulated, with steam heating external to the tubes. In any case, a substantially anhydrous ammonium nitrate melt stream 63 is produced by unit 47, which may be of any suitable configuration to accomplish this result. Stream 63 is now sprayed or otherwise dispersed into the top of prilling tower 64, which is of conventional configuration and is usually air-ventilated. Solid prills of ammonium nitrate are formed in unit 64, and the resulting product stream 65 consisting of ammonium nitrate prills is passed to product utilization, such as in fertilizer usage. As mentioned supra', the solid prills of stream 65 are of improved form and configuration, due to the presence of small amounts of solid ammonium sulfate and ammonium phosphate in the prill structure, which provide an improved form of prill structure which resists disintegration at the transition point.

Numerous alternatives within the scope of the present invention, besides those mentioned supra, will occur to those skilled in the art. The ranges of process variables enumerated supra, such as solution concentrations and pH and temperature ranges, constitute preferred embodiments for optimum utilization of the process concepts of the present invention, and the invention may be practiced outside of these ranges in suitable instances, with the exception of the pH of the solutions in units 6 and 34 formed by the respective ammoniation steps. lt will be evident that the various reaction, digestion and solids precipitation vessels may be provided with suitable mixing and agitation devices in practice, such as element 4. The precipitation of a solid calcium salt from process stream 54, with the concomitant formation of further ammonium nitrate in solution, may be attained in practice by reacting the dissolved calcium nitrate with any suitable ammonium salt having an anion which forms an insoluble salt with the calcium cation, such as ammonium sulfate. Some or all of the solids filters 9, 19, 31, 37, 44, 52 and 59 may in practice consist of any suitable device or apparatus for separating a solid phase from a liquid phase, such as a centrifugal separator, a vacuum drum filter, a plate and frame filter press or the like. The calciner 11 preferably consists of a rotary kiln, however unit 11 may alternatively consist of a fluid bed roaster or calciner or the like, which may be heated by any suitable heating means or elements. For example, unit 11 could consist of a vertically oriented fluid bed roaster, with powdered coal or other suitable fuel such as a fluid hydrocarbon fuel being directly injected into the fluid bed or added to stream 10. In some cases, the ancillary production of feed grade dicalcium phosphate as a coproduct may not be desired or warranted by market conditions, in which case stream 24 would be eliminated, with all of stream 23 passing to further processing via stream 25 and units 49, 52, 55 and 59 being omitted from the process sequence. In some instances streams 46 and 61, or stream 63,-may be directly passed to product utilization as solution-type fertilizer products of high ammonium nitrate content. If liquid stream 63 is a product of the process, it will be evident that unit 47 will be operated so as to produce stream 63 as a concentrated aqueous ammonium nitrate solution, rather than as an anhydrous melt.

An example of a batch-wise laboratory scale investigation of the process of the present invention will now be described.

EXAMPLE Ground Florida phosphate rock was employed in the laboratory scale investigation'of the process, and the optional ancillary production of feed grade dicalcium phosphate was omitted from the laboratory study. The compositions of the various principal process streams were analyzed and the analysis was reported in terms of equivalent weight percent ofthe respective component expressed as a suitable analytical product, thus phosphorus content was expressed as equivalent phosphorus pentoxide content by weight In addition, solution concentrations are expressed as percent by weight of the respective component in aqueous solution. Following are the test results of the laboratory-scale practice of the process. Table 1 presents data relative to the principal process streams bearingsignificant phosphate values, and Table ll provides data relative to the balance of the process streams employed or obtained in the batch-type laboratory investigation. Table III presents data relative to conditions'maintained in the principal process units described supra.

In summary, it will be evident that the nitrophos product obtained from unit 44 as stream 45 possesses highly valuable fertilizer characteristics, specifically with respect to total phosphate content and phosphate phate rock which comprises 1 a. digesting phosphate rock with an aqueous nitric acid stream, whereby an aqueous solution is formed at a pH'in the range of about 0.3 to 1.5 and a temperature in the range of about 55C to 80C, said solution containing dissolved phosphate, fluoride and iron phosphate,

,7 TABLE I I V PRINCIPAL soup PHOSPHATE-BEARING STREAMS Stream No. l 1 [5 38 45 A a s, grams 500 170 I35 37 262 Analys is.wt.%

T5220 ......-...fi f" H 3 -9 2 w H,O soluble BO, 0 51.0 Citrate insoluble 33.60 0.05 P105 CaO 48.00 36.0 11.9 4.50 F 3.60 10.0 2.25 7.1 0.05 Fe,o 0.80 2.30 1.0 0.08 A1,0, 1.78 5.60 8.62 0.11 0,0 0.01 0.037 Total N 1 L NH;N 10.90 so 1.54 8.70 11,0 0.10

M w TABLE 11" g,

PROCESS STREAMS EMPLOYED 0R OBTAlNED 0F NEGLIGIBLE PHOSPHATE CONTENT Stream Mass,grams 2175 275* 370 42 125 1420 6l0 175 1000' Specific gravity 0.90 0.90 1.340 Analysis,

. Total 1 ,6; 3.40 1.00 r 1.0

H20 soluble 15 0.65 CaO 34.50 0.05 F 0.02 0.01 Pep, 10.70 0.02 0.10 10,0, 0.10 0.04 0.30 $10, $8.00 Total N 0.40 23.0 Ammonium Nitrate N 21.5 so. 59.0 3.20 11,0 75 72 58 5s 60 72 30.0 HNO; 25 42 42 N11, 2s 2s 4 Volume in milliliters m b precipitating from said aqueous solution an impure 40 solid calcium phosphate precipitate containing a OPERATING CONDITIONS IN PROCESS UNIT "I J P F the fluonde and PhOSPhate Process Unit Temp. "C H d1ssolved 1n said solutlon by step (a), by addmg a 3 6 first ammonia stream in an amount of about 0.13

6 53 2, parts ammonia per part nitric acid and about 0.14

1 1 800 45 parts ammonia per part phosphate rock to said so- ;2 70 0A lution, whereby the pH of said solution is raised to '23 1.0 the range of about 2.l to about 2.5,

34 c. filtering said solution to remove precipitated soldigestion period duration was 45 minutes. I whereby q filter contalnlng Falclum F d. f... phosphate, fluorlde and iron phosphate 1s sepasolub1l1ty, as evldenced by the analys1s ata or stream rated from residual clear solution,

45 f Table 1 Supral at percent 9 d. adding a second ammonia stream to said residual the 1nput phosphate values 1s recovered in the final ni- Clea], solution, whereby the H of Said Solution is trophosphate fertlllzer product. Further phosphate va raised to the range of about 30 to 6D and Solid ues may be recovered from stream 38, as well as alufeed grade dicalcium phosphate is precipitated, um'mum frare earths l by processmg e. removing product solid feed grade dicalcium phos- Such as disclosed m 3,126,249' phate from said residual clear solution, and

we clam: I f. processing the residual clear solution from step (e) l. A process for the pr oductlon ofteed grade d1calto produce a nitrate product cium phosphate by the n1tr1cac1d acidulatlon of phos- 2. The process of claim 1, in which said residual clear solution is processed in step (f) to produce a nitrate product by adding ammonia and carbon dioxide to said residual clear solution, whereby solid calcium carbonate is precipitated, and removing solid calcium carbonate from the final residual clear solution comprising aqueous ammonium nitrate solution. 

2. The process of claim 1, in which said residual clear solution is processed in step (f) to produce a nitrate product by adding ammonia and carbon dioxide to said residual clear solution, whereby solid calcium carbonate is precipitated, and removing solid calcium carbonate from the final residual clear solution comprising aqueous ammonium nitrate solution. 